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Journal of Alloys and Compounds 462 (2008) 142–146 Chemical synthesis of nanocrystalline magnesium aluminate spinel

Journal of Alloys and Compounds 462 (2008) 142–146

Journal of Alloys and Compounds 462 (2008) 142–146 Chemical synthesis of nanocrystalline magnesium aluminate spinel via

Chemical synthesis of nanocrystalline magnesium aluminate spinel via nitrate–citrate combustion route

Ali Saberi a, , Farhad Golestani-Fard a , Hosein Sarpoolaky a , Monika Willert-Porada b , Thorsten Gerdes b , Reinhard Simon c

a Ceramic Division, Iran University of Science & Technology, Tehran, Iran b Chair of Materials Processing, University of Bayreuth, Bayreuth, Germany c Chair of Ceramic Materials Engineering, University of Bayreuth, Bayreuth, Germany

Received 21 May 2007; received in revised form 25 July 2007; accepted 25 July 2007 Available online 2 August 2007

Abstract

Nanocrystalline magnesium aluminate spinel (MgAl 2 O 4 ) was synthesized using metal nitrates, citric acid and ammonium solutions. The precursor and the calcined powders at different temperatures were characterized by X-ray diffraction (XRD), simultaneous thermal analysis (STA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The combustion mechanism was also studied by a quadrupole mass spectrometer (QMS) which coupled to STA. The generated heat through the combustion of the mixture of ammonium nitrate and citrate based complexes decreased the synthesis temperature of MgAl 2 O 4 spinel. The synthesized MgAl 2 O 4 spinel at 900 C has faced shape with crystallite size in the range of 18–24 nm. © 2007 Elsevier B.V. All rights reserved.

Keywords: Oxides; Chemical synthesis; Thermal analysis; X-ray diffraction

1. Introduction

Magnesium aluminate spinel, MgAl 2 O 4 , is a well-known material which due to excellent refractoriness, good chemical inertness, and high mechanical strength, has been widely used in various attractive applications [1–3]. The properties of obtained powder such as purity, particle size, and chemical homogeneity strongly depend on prepara- tion method. Apart from the solid-state reaction, a variety of techniques have been suggested to synthesis MgAl 2 O 4 spinel such as hydrothermal technique, plasma spray decomposi- tion of oxides, sol–gel method, combustion synthesis, freeze drying, controlled hydrolysis of metal alkoxides, and decom- position of organometallic compounds in supercritical fluids [4–9]. Recently, MgAl 2 O 4 spinel has been synthesized via citrate–nitrate route (sol–gel citrate) [10,11]. Simplicity of experimental set-up, cheapness, and good chemical homogene- ity of the synthesized powder are the main advantages of this

Corresponding author. Tel.: +49 921 55 7206; fax: +49 921 55 7205. E-mail address: ASaberi@IUST.ac.ir (A. Saberi).

0925-8388/$ – see front matter © 2007 Elsevier B.V. All rights reserved.

doi:10.1016/j.jallcom.2007.07.101

method [12]. A redox reaction between nitrate ions as an oxi- dant agent and citrate ions as a fuel agent liberates the required energy to synthesis oxide powder at lower temperatures [10]. The extensive investigations on the influence of the reactants mixture on both phase composition and microstructure of the obtained MgAl 2 O 4 spinel have been done; however, the mech- anism of the combustion synthesis is still not well understood. In this study MgAl 2 O 4 spinel powder was synthesized using citrate–nitrate route and the combustion mechanism and gaseous products of combustion reactions were studied by quadrupole mass spectrometry measurements.

2. Experimental procedure

Magnesium nitrate (Mg(NO 3 ) 2 ·6H 2 O), aluminum nitrate (Al(NO 3 ) 3 · 9H 2 O), citric acid (C 6 H 8 O 7 ·H 2 O), and ammonia solution (NH 4 OH, 30%) were used as the starting materials to synthesis MgAl 2 O 4 spinel. All chemical mate- rials were supplied from Merck Co. Germany. To prepare a transparent sol, 0.021 mol of magnesium nitrate and 0.042 mol of aluminum nitrate were dissolved in 100 ml of distilled water. Then citric acid as chelating-fuel agent was added to the solution. The molar ratio of citrate to metallic ions in the solution was maintained at 0.5:1. Citric acid has two different roles. (1) Citric acid as a chelating agent binds metallic ions (Al 3+ & Mg 2+ ) and prohibits precipitation of solution during changing pH. (2) Citric acid as a fuel

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143

helps to progress the synthesis at relatively low temperatures [13]. The solution was agitated using a magnetic stirrer at room temperature for 1 h. To increase the efficiency of chelating agent, citric acid, pH of the solution was adjusted to six by adding ammonia drop-wisely [14,15]. This solution was gelled by in situ formation of polyacrylamide network while heating the primary sol at 120 C. By further heating, the citric acid melts at around 173 C and converts to aconitic acid (reaction (R.1)). The aconitic acid then converts to itaconic acid according to reaction (R.2). The itaconic acid (melting point 166 C), upon continued heating, undergoes polymerization and swells with the decarboxylation (releas- ing CO 2 ) [14]. Thus, the gel was heated at 180 C in an electric oven to get a pale yellowish mass. Then the obtained mass, hereinafter referred to as precursor, was ground into powder by a pestle and mortar and subsequently heat-treated in an atmosphere control furnace at various temperatures for 1 h with a heating rate of 10 C/min and 50 ml/min dry air flow rate.

C 6 H 8 O 7

C 6 H 6 O 6 +

C 6 H 6 O 6 C 5 H 6 O 4 +

H 2 O

(R.1)

CO 2

(R.2)

Differential scanning calorimetry (DSC) and thermogravimetric (TG) anal- yses of precursor were carried out with a Netzsch STA-449C with a heating rate of 10 C/min in a continuous air flow (50 ml/min). Concurrently, the gases exiting the STA cell were analyzed by a quadrupole mass spectrometer (QMS). In order to avoid throwing out any amount of solid product when the gases leave the specimen under analysis, a lid with a little hole was put on the crucible. Phase evaluation of the calcined precursor at different temperatures was studied using a Philips (PW-3040) diffractometer with Cu K radiation. JCPDS cards 21-1152 and 47-0867 were used for identification of MgAl 2 O 4 spinel and NH 4 NO 3 (ammonium nitrate), respectively. The crystallite size of the MgAl 2 O 4 spinel powder was determined using Scherrer equation (Eq. (1)):

L =

β(2θ) cos θ 0

(1)

where λ is the wavelength (=0.15406 nm), θ 0 the Bragg angle, k the constant (=0.94), and L is the crystallite size. The half-width of the diffraction line β(2θ) (in radians) was taken as the experimental half-width (β exp ) and was corrected for experimental broading (β instr ) according to Eq. (2) [16]:

β(2θ) = (β

2

exp β instr ) 1/2

2

(2)

β instr was measured experimentally by a silicon powder. FTIR spectra were obtained by a Shimadzu FTIR-8400S ® spectrophotome- ter. Further, field emission scanning electron microscope (LEO ® 1530, FE-SEM) and transmission electron microscope (LIBRA ® 200, TEM) were used for microstructural observation. The surface area of synthesized powders was measured with an ASAP-2010, Gimini according to BET technique.

3. Results and discussion

The X-ray diffraction patterns of the precursor and the cal- cined powders at different temperatures are shown in Fig. 1. According to XRD results, the precursor is a mixture of amor- phous matrix and crystalline ammonium nitrate (NH 4 NO 3 ) (Fig. 2a). Ammonium nitrate forms from the reaction of ammo- nium cations (NH 4 + ) with nitrates (NO 3 ) corresponding to

+ ) with nitrates (NO 3 − ) corresponding to Fig. 1. XRD patterns of the

Fig. 1. XRD patterns of the dried and calcined precursor at different tempera- tures, precursor (a), 300 C (b), 400 C (c), 500 C (d), 600 C (e), 700 C (f), 900 C (g), 1000 C (h), and 1100 C (i).

reaction (R.3). The peaks related to ammonium nitrate dis- appear in the calcined powder at 300 C. The XRD pattern shows MgAl 2 O 4 spinel formation at around 400 C. As calcina- tion temperature increases, gradual increase in peak intensities accompanied by sharpening of the peaks is observed, which indicates the crystallite size of spinel is arising.

Al(NO 3 ) 3 +

Mg(NO 3 ) 2 + 5NH 4 OH Al(OH) 3 +

(R.3)

Table 1 presents the approximate crystallite size and charac- teristics of the spinel powders calcined at different temperatures. Three diffraction peaks (3 1 1), (4 0 0), and (4 4 0) were chosen for measuring the crystallite size. The average crystallite size of calcined spinel at 900 C is in the range of 18–20 nm. The lat- tice constant of the synthesized MgAl 2 O 4 spinel above 900 C

Mg(OH) 2 + 5NH 4 NO 3

˚

is about 8.08 A, which is in agreement with JCPDS cart No.

21-1152.

The simultaneous thermal analysis (DSC-TG) of the precur- sor has been shown in Fig. 2a. The small endothermic peak about 170 C in DSC accounted for 20 wt.% of the initial weight loss in TG, is assigned to the dehydration of the precursor. QMS results also prove the evaporation of H 2 O at this temperature range (Fig. 2b). The outstanding and sharp exothermic peak at around 280 C with a 70 wt.% corresponding weight loss is due to combustion of ammonium nitrate and citrates. These exothermic reactions

Table 1 The approximate crystallite size and characteristics of the MgAl 2 O 4 powder calcined at different temperatures for 1 h

 

˚

˚

˚

˚

T

( C)

d 311 (

A)

D (nm)

d 400 ( A)

D (nm)

d 440 ( A)

D (nm)

Ave. lattice constant ( A)

700

2.449

9

2.063

10

1.464

10

8.218

900

2.438

19

2.028

21

1.432

18

8.102

1000

2.437

28

2.023

27

1.429

29

8.087

1100

2.437

37

2.022

38

1.427

41

8.084

144

A. Saberi et al. / Journal of Alloys and Compounds 462 (2008) 142–146

al. / Journal of Alloys and Compounds 462 (2008) 142–146 Fig. 2. (a) STA curves of

Fig. 2. (a) STA curves of MgAl 2 O 4 spinel precursor, QMS curves of (b) H 2 O, (c) CO + N 2 , (d) CO 2 + N 2 O, (e) NO 2 , (f) NO, and (g) O 2 .

tack place very quickly, involving the rapid formation of rather large quantity of gaseous products like NO, N 2 O, NO 2 , N 2 , O 2 , CO, CO 2 , and H 2 O (Fig. 2b–g). In spite of NO, N 2 O, NO, and NO 2 gases exiting in a short range of temperature (280–300 C),

the QMS results related to N 2 + CO (a.m.u. = 28) show a broad peak at the range of 280–340 C (Fig. 2c). Therefore, it can be concluded that at the first ammonium nitrate decomposes at around 280 C and consequently the resulted heat helps com-

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145

bustion of citrates. The combustion of citrates is accompanied by evolution CO (g) and CO 2 (g) (Fig. 2c and d). According to the literature, ammonium nitrate can decompose between 260 and 300 C at 760 mmHg pressure. Its thermal decomposition can occur in a complex way. Some of the possible reactions of ammonium nitrate decomposition are listed below ((R.4)–(R.7))

[12,17]:

NH 4 NO 3

(3/4)N 2 + (1/2)NO 2 + 2H 2 O (R.4)

NH 4 NO 3 (1/2)N 2 + NO + 2H 2 O (R.5)

(R.6)

NH 4 NO 3 N 2 + 2H 2 O + (1/2)O 2 (R.7)

However, it seems that all of the above reactions ((R.4)–(R.7)) take place during the combustion, the lower amount of N 2 O and O 2 gases in exiting gases in comparison with NO, NO 2 , and N 2 gases states that ammonium nitrate decomposition happened mostly via (R.4) and (R.5). Further heating produces a small and broad exothermic peak at around 390 C, which corresponds to the crystallization of MgAl 2 O 4 spinel. The crystallization temperature of MgAl 2 O 4 is lower than the reported results by the others used similar synthesis technique [10,11]. The third exothermic peak (550 C) is due to the oxidation of residue car- bon admitted by the results of QMS showing the presence of CO (g) at this temperature range (530–560 C) (Fig. 2c). How- ever, the most amount of carbon has been oxidized while the first exothermic reaction at 280 C. Fig. 3 displays the recorded IR spectra for the precursor and the calcined powders at 500, and 900 C. Common bands are

NH 4 NO 3 N 2 O + 2H 2 O

bands are NH 4 NO 3 → N 2 O + 2H 2 O Fig. 3.

Fig. 3. FTIR spectra of precursor (a), the calcined powders at 500 C (b), and

900 C (c).

powders at 500 ◦ C (b), and 900 ◦ C (c). Fig. 4. FE-SEM micrograph of

Fig. 4. FE-SEM micrograph of MgAl 2 O 4 spinel powder calcined at 900 C.

seen in precursor spectrum (Fig. 3a) such as the broad –OH band centered around 3400 cm 1 and the 1630 cm 1 H 2 O vibration band. The peaks at around 2800–2900 cm 1 related to stretch- ing C–H vibrations are coming from the organic compounds (citrates) used along the synthesis. The peaks appearing at 1384 cm 1 and 829 cm 1 correspond to vibration modes of NO 3 groups. In the calcined sample at 500 C (Fig. 3b) C–H groups are still present but in the calcined powders at higher tempera- tures (Fig. 3c), all organic bands are disappeared and inorganic band at 600 cm 1 corresponding to the metal–oxygen–metal bond (M–O–M), become sharper and stronger [18,19]. FE-SEM micrograph (Fig. 4) depicts agglomerated particles morphology of the calcined powder at 900 C. The synthesized powder has faced shape and in spite of partial agglomeration of the calcined powder, the size of agglomerates is in the range of 100–300 nm. Fig. 5 illustrates the specific surface area of synthesized MgAl 2 O 4 spinel at different temperatures. By increasing the calcination temperature, due to neck formation between par- ticles, the value of specific surface area of samples shows a dramatic decrease. The released heat during the combustion

a dramatic decrease. The released heat during the combustion Fig. 5. BET surface area of the

Fig. 5. BET surface area of the synthesized MgAl 2 O 4 spinel powder at different temperatures for 1 h.

146

A. Saberi et al. / Journal of Alloys and Compounds 462 (2008) 142–146

al. / Journal of Alloys and Compounds 462 (2008) 142–146 Fig. 6. Bright field TEM micrograph

Fig. 6. Bright field TEM micrograph and SAEDP of MgAl 2 O 4 spinel powder calcined at 900 C.

brings down the crystallization temperature of the magnesium aluminate spinel. Actually the main benefit of nitrate–citrate synthesis technique is short period of synthesis. The fast and low temperature synthesis prohibit the powder from sintering, thus the obtained powder has higher surface area as well as good sinterability in comparison with other common synthesis techniques [12]. Magnesium aluminate spinel powder resulting from the com- bustion reactions, were characterized by TEM (Fig. 6). The bright field TEM image and selected area electron diffraction pattern (SAEDP) of synthesized powder at 900 C show that the synthesized MgAl 2 O 4 spinel is polycrystalline with crystal- lite size in the range of 20–25 nm. The observed results are in good corresponding to the calculated crystallite size by Scherrer equation.

4. Conclusion

Nanocrystalline magnesium aluminate spinel (MgAl 2 O 4 ) was synthesized by an auto-ignition process using citric acid, metal nitrates, and ammonia at relatively low temperatures. The initial crystallization temperature of MgAl 2 O 4 spinel was at 400 C, whereas that of the fully crystallized magnesium alu- minate spinel appeared at temperatures above 900 C. The mechanism of combustion synthesis of magnesium alu- minate spinel was studied. The results showed that by increasing the calcination temperature beyond 280 C, ammonium nitrate suddenly decomposes due to a redox reaction between excess nitrate ions and citrate ions. Then the released heat helps com- bustion of citrates. The generated heat of the combustion of ammonium nitrate as well as citrates helps to synthesis magne- sium aluminate spinel at relatively lower temperatures.

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